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WO2019028436A1 - Compositions d'encres conductrices comprenant de l'or et leurs procédés de préparation - Google Patents

Compositions d'encres conductrices comprenant de l'or et leurs procédés de préparation Download PDF

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Publication number
WO2019028436A1
WO2019028436A1 PCT/US2018/045277 US2018045277W WO2019028436A1 WO 2019028436 A1 WO2019028436 A1 WO 2019028436A1 US 2018045277 W US2018045277 W US 2018045277W WO 2019028436 A1 WO2019028436 A1 WO 2019028436A1
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Prior art keywords
gold
acid
ink composition
salt
iii
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PCT/US2018/045277
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English (en)
Inventor
Steven Brett Walker
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Electroninks Inc
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Electroninks Inc
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Publication date
Application filed by Electroninks Inc filed Critical Electroninks Inc
Priority to JP2020505783A priority Critical patent/JP2020529710A/ja
Priority to US16/636,150 priority patent/US20200157369A1/en
Publication of WO2019028436A1 publication Critical patent/WO2019028436A1/fr
Anticipated expiration legal-status Critical
Priority to JP2022119494A priority patent/JP2022136229A/ja
Priority to JP2024075267A priority patent/JP2024102240A/ja
Priority to US18/806,544 priority patent/US20250223456A1/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/36—Inkjet printing inks based on non-aqueous solvents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic

Definitions

  • the present disclosure is related generally to compositions of conductive gold ink and methods for making the same.
  • Precursor-based inks are based on thermally unstable precursor complexes that reduce to a conductive metal upon heating.
  • Prior particle- and precursor-based methods generally rely on high temperatures to form conductive coatings and thus may not be compatible with substrates that require low processing temperatures to maintain integrity.
  • What is needed in the art are better compositions and methods for creating high quality conductive metal ink at a conversion temperature that is lower than that of existing conductive ink compositions such as a silver-based ink.
  • ink compositions that are stable and can be stored at room temperature.
  • ink compositions for making a conductive gold structure.
  • the ink compositions comprise: a gold salt; and a complexing agent, optionally further comprising a short chain carboxylic acid or salt thereof, wherein the gold salt is a carboxylate, or the gold salt is capable of forming a carboxylate with the short chain carboxylic acid or with a salt thereof.
  • the gold salt is a gold (I) salt, a gold (II) salt, or a gold (III) salt.
  • the gold salt is or comprises gold(III) formate, gold(III) acetate, gold(III) propionate, gold(III) lactate, gold(III) oxalate, gold(III) carbonate, gold(III) nitrate, gold(III) nitrite, gold(III) phosphate, gold(III) oxide, gold(III) fluoride, gold(III) bromide, gold(I) chloride, gold(III) chloride, gold(III) chloride trihydrate, gold(III) hydroxide, gold(I) iodide, hydrogen tetrabromoaurate(III) hydrate, potassium gold(III) chloride, or gold(III) terephthalate.
  • the gold salt is a gold carboxylate.
  • the molar ratio of complexing agent to the gold salt is around 6: 1.
  • the complexing agent is or comprises an alkyl amine or ammonia.
  • the alkyl amine is or comprises a primary amine, a secondary amine, or a polyamine.
  • the alkyl amine is selected from the group consisting of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, amylamine, isoamylamine, dipentylamine, and combinations thereof.
  • the alkyl amine is selected from the group consisting of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, amylamine, dipentylamine, and combinations thereof.
  • the short chain carboxylic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, lactic acid, oxalic acid, citric acid, and citraconic acid.
  • the citraconic acid is generated from citraconic anhydride.
  • the short chain carboxylic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, lactic acid, oxalic acid, and citric acid.
  • the composition further comprises methylene diamine or ethylene diamine.
  • the composition further comprises a solvent selected from the group consisting of ethanol, butanol, propylene glycol, water, and combinations thereof.
  • the gold salt is gold(III) formate
  • the complexing agent is selected from the group consisting of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, amylamine, dipentylamine, ammonia, and combinations thereof.
  • the complexing agent is selected from the group consisting of methylamine, dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine, butylamine, dibutylamine, amylamine, dipentylamine, ammonia, and combinations thereof, and the short chain carboxylic acid is acetic acid.
  • the composition further comprises ethylene diamine.
  • the composition further comprises a solvent selected from the group consisting of ethanol, butanol, propylene glycol, water, and combinations thereof.
  • ink compositions for making a conductive structure comprising gold.
  • the ink compositions comprise: a gold salt of an organic acid; a monomeric building block; and a solvent having a boiling point of about 160 °C or less; where the conjugate base of the organic acid reacts with the monomeric building block to form a polymer while ionic gold is reduced to elemental gold.
  • the polymer is a polyamide, a polyimide, a polyamideimide, or a polyester.
  • the organic acid comprises a dicarboxylic acid selected from the group consisting of oxalic acid (ethanedioic acid), malonic acid
  • the monomeric building block comprises a diamine, an N-silylated diamine, or a diisocyanate.
  • the diamine comprises a linear aliphatic diamine, a branched aliphatic diamine, a cyclic aliphatic diamine, or an aromatic diamine.
  • the monomeric building block is selected from the group consisting of ethylenediamine (1 ,2-diaminoethane), an N-alkylated diamine, 1, 1- dimethylethylenediamine, 1 , 1 -dimethylethylenediamine, tetramethylethylenediamine (TMEDA), ethambutol, TMEDA, 1 ,3-diaminopropane (propane- 1,3-diamine), putrescine (butane- 1,4-diamine), cadaverine (pentane-l,5-diamine), or hexamethylenediamine
  • the polymer is a polyimide formed from a poly(amic acid) precursor, a polyisoimide precursor, a mixture of a diester-acid and a diamine, a mixture of a tetracarboxylic acid and a diamine, a mixture of a dianhydride and a diisocyanate, a polyetherimide via a nucleophilic aromatic substitution reaction, or a mixture of 4,4'- methylenediphenyldiisocyanate (MDI) and trimellitic anhydride (TMA).
  • MDI 4,4'- methylenediphenyldiisocyanate
  • TMA trimellitic anhydride
  • the polyester is selected from the group consisting of polyethylene adipate (PEA), polybutylene succinate (PBS), poly(3- hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and Vectran.
  • PEA polyethylene adipate
  • PBS polybutylene succinate
  • PHBV poly(3- hydroxybutyrate-co-3-hydroxyvalerate)
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PTT polytrimethylene terephthalate
  • PEN polyethylene naphthalate
  • Vectran Vectran
  • conductive structures comprising gold.
  • the methods comprise: providing a metal salt composition comprising a gold salt and a complexing agent; adding a short chain carboxylic acid or a salt of the short chain carboxylic acid to the combined metal salt composition and complexing agent to form an ink composition; optionally partially evaporating the complexing agent from the ink composition to form a concentrated formulation; and reducing the metal salt composition to form a conductive structure comprising gold, wherein the concentrated formulation and the conductive structure comprising gold are formed at a temperature of about 160 °C or less.
  • the temperature is about 140 °C or less.
  • the short chain carboxylic acid or the salt of the short chain carboxylic acid is not added until after the gold salt is dissolved in the complexing agent.
  • the method further comprises depositing the ink composition onto a substrate.
  • the ink composition is deposited onto the substrate by a method selected from the group consisting of spray processing, dip coating, spin coating, inkjet printing, and e-jet printing.
  • the method further comprises depositing the concentrated formulation onto a substrate.
  • the concentrated formulation is deposited onto the substrate by a method selected from the group consisting of screen printing, roll-to-roll processing, and direct ink writing.
  • a method selected from the group consisting of screen printing, roll-to-roll processing, and direct ink writing is deposited onto the substrate by a method selected from the group consisting of screen printing, roll-to-roll processing, and direct ink writing.
  • disclosed herein are alternative methods of making conductive structures comprising gold. The methods comprise: providing a gold salt of an organic acid and a monomeric building block; and causing polymer formation between the conjugate base of the organic acid and the monomeric building block.
  • precursor-based gold conductive ink compositions preferably having one or more of the following characteristics.
  • Second, the elemental gold generated from the ink composition is pure and not contaminated with by-products.
  • the ink composition may possess low viscosity, so that it is compatible with a broad range of patterning techniques, including direct ink writing, inkjet printing, and airbrush spraying.
  • Fourth, the patterned features prepared using the ink composition may be highly conductive at room temperature and achieve bulk conductivity upon annealing at mild temperatures (e.g. , ⁇ 140 °C).
  • conductive ink composition As used herein, the terms “conductive ink composition”, “conductive ink”, “ink composition”, “ink”, or variations thereof, can be used interchangeably.
  • a conductive "gold ink composition” refers to ink compositions including, but not limited to, a gold salt.
  • a conductive gold ink composition may comprise another metal salt; for example, a palladium salt can be added to promote stability of the conductive ink.
  • a gold conductive structure is obtained through a gold-catalyzed amidation reaction.
  • a gold salt e.g. , a gold carboxylate salt
  • the amine reacts with the carboxyl group in the gold carboxylate to form an amide, and ionic gold is reduced to the elemental form.
  • the amine functions as both a complexing agent and as a reducing agent.
  • the above-described gold-catalyzed amidation reaction can take place at a temperature around 120 °C. At such a temperature, all the liquid products are evaporated, leaving only conductive elemental gold. In some cases, however, it may be advantageous for the reaction to be run at lower temperatures, for example around 100 °C, around 80 °C, around 60 °C, or at even lower temperatures.
  • the instant inventor has discovered that the temperature of the reaction can be modulated by the choice of carboxylic acid used to form the gold carboxylate. For example, the reaction temperature can be as low as 60 °C, or even lower, by selection of an appropriate carboxylic acid for use in the ink composition.
  • liquid products may remain after formation of the elemental gold. The remaining liquid products may be removed by evaporation in a subsequent step or may be removed by other means, as appropriate for the situation and conditions.
  • ink compositions for making a conductive gold structure comprising: a gold salt, and a complexing agent, optionally further comprising a short chain carboxylic acid or salt thereof, wherein the gold salt is a carboxylate, or the gold salt is capable of forming a carboxylate with the short chain carboxylic acid or with the salt thereof.
  • the disclosure provides ink compositions for making a conductive gold structure, the ink compositions comprising: a gold salt; and one of (a) a complexing agent; (b) a complexing agent and a short chain carboxylic acid, or (c) a complexing agent and a salt of a short chain carboxylic acid, wherein the gold salt is a carboxylate, or the gold salt is capable of forming a carboxylate with the short chain carboxylic acid or with a salt thereof.
  • Gold salts finding use in the instant compositions include without limitation gold(III) formate, gold(III) acetate, gold(III) propionate, gold(III) lactate, gold(III) oxalate, or a mixture of these.
  • gold(III) butyrate and gold(III) pentanoate can also be used if the reaction temperature is higher.
  • the reaction temperature is 180 °C or lower, 170 °C or lower, 160 °C or lower, 150 °C or lower, 140 °C or lower, 130 °C or lower, 120 °C or lower, 110 °C or lower, 100 °C or lower, 90 °C or lower, or 80 °C or lower. In some embodiments, the reaction temperature may be higher than 180 °C.
  • the only conductive material in the gold ink composition is gold.
  • multiple conductive materials are included in a gold ink; for example, palladium can be used as a stabilizing agent. Additional information on the stabilizing property of palladium can be found in U.S. Provisional Patent Application No. 62/540,829, filed August 3, 2017 and entitled "Conductive Ink Compositions Comprising Palladium and Methods for Making the Same", which is hereby incorporated by reference in its entirety.
  • the complexing agent is an alkyl amine.
  • the gold salt is dissolved in the alkyl amine.
  • An alkyl amine is an amino group substituted by at least one C 1-8 alkyl group, where an alkyl group refers to a hydrocarbon group which may be linear, cyclic, or branched or a combination thereof having the number of carbon atoms designated (i.e., C 1-8 means one to eight carbon atoms).
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, pentyl, isopentyl, cyclohexyl, cyclopentyl, and the like.
  • An alkyl amine may be a primary, secondary or tertiary amine, preferably a primary amine.
  • one or more of the carbon atoms in the alkyl group can be substituted with a heteroatom, such as an oxygen, a sulfur, or a nitrogen.
  • the alkyl amine which is a weak base, acts as a reducing agent for the gold salt through an amidation reaction. Additionally, it also functions as a stabilizer and solvent for the gold salt. Any suitable alkyl amine that reduces or stabilizes the gold salt or additional metal salt may be employed.
  • the alkyl amine has a boiling point of about 140 °C or less. In some embodiments, the alkyl amine has a boiling point of about 120 °C or less. In some embodiments, the alkyl amine has a boiling point of about 100 °C or less.
  • alkyl amines having a boiling point of about 120 °C or less include but are not limited to isomers of C 6 Hi5N, isomers of C5H13N, isomers of C4H11N, isomers of C3H 9 N, isomers of C2H7N, and isomers of CH5N.
  • alkyl amines having boiling points between about 40 °C and 180 °C include, but are not limited to methylamine, ethylamine, aniline, propylamine, n-butyl amine, amylamine, isoamylamine, s-butylamine, iso-butylamine, isopentylamine, 1 - methylbutylamine, 1 -amino-2-methylbutane, N-methyldiethylamine, diethylamine, di propylamine, dibutylamine, and dipentylamine.
  • Alkyl amines comprising ether linkages for example methoxyethyl amine and the like, are also considered suitable for use in the instant compositions.
  • the amine is propylamine, n-butyl amine, or amylamine; more preferably propylamine or n-butylamine.
  • the alkyl amine is selected from the group consisting of methylamine, ethylamine, propylamine, butylamine, amylamine,
  • the alkyl amine is selected from the group consisting of methylamine, ethylamine, propylamine, butylamine, and amylamine.
  • the alkyl amine may be selected based on its boiling point for a specific application. For deposition methods such as inkjet printing or e-jet, greater stability is generally preferred, and thus it may be preferable to use an alkyl amine with a higher boiling point such as amyl amine which has a boiling point of about 104 °C. In some aspects it may be desirable to add a short chain diamine (e.g., methylenediamine or ethylenediamine) in addition to the alkyl amine to provide even more stability. However, when ethylenediamine is used alone, the electrical conductivity of the resulting gold- containing product may not be as high as desired.
  • a short chain diamine e.g., methylenediamine or ethylenediamine
  • alkyl amine and ethylenediamine such as amyl amine with ethylenediamine in a given ratio to prepare the gold-based ink.
  • the ratio of alkyl amine to ethylenediamine may fall in the range from about 4: 1 to about 1 :4 on a volume: volume basis, and is preferably about 1 : 1.
  • Another short chain diamine such as, for example, methylenediamine may be used instead of, or in addition to, ethylenediamine.
  • alkyl amine can be added to promote the amidation reaction between the short chain gold carboxylate and the alkyl amine.
  • an excess of alkyl amine is used relative to the short chain carboxylic acid to ensure that the short chain carboxylic acid is complexed and thereby unavailable to act as a reducing agent.
  • the molar ratio of the alkyl amine to the short chain carboxylate is at least about 1 : 1 , preferably at least about 3: 1, more preferably at least about 6: 1. In some embodiments, the molar ratio of the alkyl amine to the short chain carboxylate is greater than 6: 1.
  • alkyl amine may be added to dissolve the gold salt or any additional metal salt.
  • the amount of alkyl amine required may be determined by slowly adding the alkyl amine to the gold salt and any additional metal salt and monitoring the dissolution of the gold salt and any additional metal salt. In some aspects, about 2 mL of alkyl amine may be used to dissolve about 1 g of gold salt or any additional metal salt.
  • Other methods known to one skilled in the art to assist in dissolution of the gold salt and any additional metal salt including addition of a solvent or other component such as a higher molecular weight alkyl amine or a diamine to assist in dissolution are also contemplated.
  • a solvent to the mixture of the alkyl amine and gold salt (and any additional metal salt).
  • the solvent preferably has a boiling point of at most 180 °C.
  • suitable solvents include water, alcohols (including for example, methanol, ethanol, 1-propanol, and 2-propanol), esters, ketones, and ethers.
  • the solvent is water, ethanol, butanol, or propylene glycol.
  • the solvent may include two or more co-solvents.
  • the solvent may include water and another co-solvent such as butanol or propylene glycol.
  • the complexing agent is ammonium hydroxide (e.g. , ammonia or aqueous ammonia).
  • ammonium hydroxide e.g. , ammonia or aqueous ammonia.
  • the gold salt and any additional metal salt, if applicable
  • the ammonium hydroxide acts as a stabilizer and solvent for the gold salt (and any additional metal salt, if applicable).
  • the ammonium hydroxide is not intended to act as a reducing agent for the gold ink composition (i.e. , it does not appreciably reduce the gold salt or any additional metal salt, if applicable).
  • a short chain carboxylic acid can be added to the composition (e.g. , in addition to gold carboxylate salt and alkyl amine).
  • the short chain carboxylic acid is added to form an ink formulation.
  • the short chain carboxylic acid can function as the reducing agent for the gold salt (and any additional metal salt, if applicable).
  • a salt e.g. , an ammonium salt
  • the short chain carboxyhc acid may be added to form the ink formulation.
  • the salt of the short chain carboxyhc acid may function as the reducing agent for the gold salt (and any additional metal salt, if applicable), generally as described herein with reference to the short chain carboxyhc acid. Without wishing to be bound by theory, it is believed that by adding the short chain carboxyhc acid in the presence of the complexing agent, an acid-base complex is formed between the short chain carboxyhc acid and the complexing agent, thereby preventing the short chain carboxyhc acid from reducing the gold salt (and any additional salt, if applicable) immediately.
  • the short chain carboxyhc acid becomes liberated and reduction of the gold salt to elemental gold (gold in the zero oxidation state) by the short chain carboxyhc acid may occur.
  • additional metal salts e.g. , a silver salt or a palladium salt
  • the additional metal salt(s) will be reduced to their corresponding elemental metal forms too.
  • the short chain carboxyhc acid can have a chain length of seven carbons or less and typically has a chain length of five carbons or less.
  • Examples of short chain carboxyhc acids include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, and pentanoic acid.
  • the short chain carboxyhc acid has a chain length of two carbons or less. More preferably the short chain carboxyhc acid is formic acid.
  • Formic acid has been found to be particularly advantageous due to its low boiling point and volatile byproducts.
  • Formic acid comprises an aldehyde functionality, which enhances its reducing ability.
  • short chain carboxyhc acids comprising an aldehyde functionality are preferred short chain carboxyhc acids.
  • formic acid may result in the formation of carbon dioxide and water, leaving no residual reducing agent.
  • the short chain carboxyhc acid is a reducing agent for the gold salt (or any additional metal salt, when applicable), but due to the complexation with the complexing agent that occurs upon adding the short chain carboxylic acid to the mixture, the acid is substantially prevented from reducing the gold salt.
  • reduction of the gold salt does not occur until the complexing agent is partially or completely evaporated from the ink formulation.
  • the complexing agent may be evaporated after deposition of the ink formulation onto a desired substrate, at which time the acid reduces the gold salt to form a conductive gold coating or other gold structure on the substrate.
  • the complexing agent may be partially evaporated from the ink during a further processing step in order to increase the viscosity of the ink and form a concentrated formulation for use in a printing technique such as direct ink writing.
  • partial reduction of the gold salt may occur prior to deposition, such that the ink may have a composite structure including a mixture of unreacted gold salt along with conductive gold particles (e.g. , nanocrystals) formed during the partial reduction.
  • the viscosity of such a composite ink may be tailored for printing techniques such as direct ink writing, where the ink must span gaps during fabrication of three-dimensional structures.
  • Evaporation of the complexing agent typically occurs at an elevated temperature below about 120 °C, or between about 50 °C and 100 °C, or between about 60 °C and 90 °C.
  • the evaporation may occur over a period of minutes or hours, depending on the volatility of the complexing agent and the temperature at which the evaporation is carried out.
  • the complexing agent may also be evaporated at room temperature over a longer time period. In some cases, the evaporation may be performed under reduced pressure.
  • UV light may also be used to accelerate the reaction instead of heat, since UV light will reduce silver salts.
  • a solvent to the mixture of the ammonium hydroxide and gold salt (and any additional metal salt, if applicable).
  • the solvent preferably has a boiling point of at most 160 °C.
  • suitable solvents include water, alcohols (including for example, methanol, ethanol, 1- propanol, and 2-propanol), esters, ketones, and ethers.
  • the solvent is water or ethanol.
  • particle formation may only occur after patterning, as evaporation ensues.
  • a highly conductive gold structure remains after the reduction, even at low processing temperatures, because the low boiling points of non-gold constituents allow for a controlled and complete, or nearly complete, removal of the non-gold constituents.
  • the gold conductive structure is obtained through gold catalyzed polymerization.
  • elemental gold can be formed by combining the gold salt of an organic acid with a monomeric building block, where the conjugate base of the organic acid reacts with the monomeric building block to form a polymer material, while yielding elemental gold.
  • the resulting polymer is a polyamide.
  • the resulting polymer is a polyimide.
  • the resulting polymer is a polyamideimide.
  • the resulting polymer is a polyester.
  • the polyamide is formed between a gold salt of an organic acid and a diamine. In some embodiments, the polyamide is formed by a diisocyanate and a gold salt of an organic acid.
  • the organic acid is a dicarboxylic acid.
  • Exemplary dicarboxylic acids include but are not limited to oxalic acid (ethanedioic acid), malonic acid (propanedioic acid), succinic acid (butanedioic acid), glutaric acid
  • the organic acid is terephthalic acid.
  • the monomeric building block is a diamine. In some embodiments, the monomeric building block is an N-silylated diamine. In some embodiments, the monomeric building block is a diisocyanate.
  • the diamine is a linear aliphatic diamine, including, but not limited to, ethylenediamine (1,2-diaminoethane), an N-alkylated diamine, 1, 1-dimethylethylenediamine, 1, 1-dimethylethylenediamine, tetramethylethylenediamine (TMEDA), ethambutol, TMEDA, 1,3-diaminopropane (propane- 1,3-diamine), putrescine (butane- 1,4-diamine), cadaverine (pentane-l,5-diamine), or hexamethylenediamine (hexane-l,6-diamine).
  • ethylenediamine 1,2-diaminoethane
  • N-alkylated diamine 1, 1-dimethylethylenediamine, 1, 1-dimethylethylenediamine, tetramethylethylenediamine (TMEDA), ethambutol, TMEDA, 1,3-diamin
  • the diamine is a branched aliphatic diamine, including, but not limited to, ethylenediamine or derivatives thereof such as 1 ,2- diaminopropane, diphenylethylenediamine, or trans- 1 ,2-diaminocyclohexane.
  • the diamine is a cyclic aliphatic diamine such as 1 ,4-Diazacycloheptane.
  • the diamine is a xylylenediamine including, but not limited to, o-xylylenediamine (OXD), m-xylylenediamine (MXD), or p- xylylenediamine (PXD).
  • the diamine is an aromatic diamine, including, but not limited to, o-phenylenediamine (OPD), m-phenylenediamine (MPD), p- phenylenediamine (PPD), or 2,5-diaminotoluene (which is related to PPD but contains a methyl group on the ring).
  • OPD o-phenylenediamine
  • MPD m-phenylenediamine
  • PPD p- phenylenediamine
  • 2,5-diaminotoluene which is related to PPD but contains a methyl group on the ring.
  • the diamine includes various N-methylated derivatives of the phenylenediamines such as imethyl-4-phenylenediamine or N,N'-di-2- butyl- 1 ,4-phenylenediamine.
  • the diamine includes a diamine with two aromatic rings and derivatives thereof such as 4,4'-diaminobiphenyl or 1,8- diaminonaphthalene.
  • the diisocyanate includes, but is not limited to, toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), methyl isocyanate (MIC), or isophorone diisocyanate (IPDI).
  • TDI toluene diisocyanate
  • MDI methylene diphenyl diisocyanate
  • HDI hexamethylene diisocyanate
  • MIC methyl isocyanate
  • IPDI isophorone diisocyanate
  • the polymer is a polyimide derivatized from poly(amic acid) precursors.
  • the polyimide is formed from polyisoimide precursors.
  • the polyimide is formed from a diester- acid and a diamine.
  • the polyimide is formed from a tetracarboxylic acid and a diamine.
  • the polyimide is formed from a dianhydride and a diisocyanate.
  • the polyimide is formed from a polyetherimide via a nucleophilic aromatic substitution reaction.
  • the polymer is a polyamideimide formed between, for example, 4,4'- methylenediphenyldiisocyanate (MDI) and trimellitic anhydride (TMA).
  • MDI 4,4'- methylenediphenyldiisocyanate
  • TMA trimellitic anhydride
  • the polymer is a polyester formed between a gold salt of a dicarboxylic acid and a diol.
  • Exemplary polyester includes polyethylene adipate (PEA), polybutylene succinate (PBS), poly(3-hydroxybutyrate-co-3- hydroxyvalerate) (PHBV), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN) or Vectran.
  • a solvent to the polymerization mixture of gold salt and monomeric building blocks.
  • the solvent preferably has a boiling point of at most 160 °C.
  • suitable solvents include water, alcohols (including for example, methanol, ethanol, 1-propanol, and 2-propanol), esters, ketones, and ethers.
  • the solvent is water or ethanol.
  • Gold ionic inks can be made by complexation with 6 nitrogens from groups consisting of ammonia, primary amines, secondary amines, or polyamines and a stoichiometric amount of a carboxylate counter-ion to the ionic valence of the gold species.
  • a carboxylate counter-ion typically gold (III) acetate could be dissolved in ammonia or amines to create the corresponding amide at moderate temperatures (80-140 °C).
  • Other carboxylate counter-ions could be used such as polycarboxylates or other single carboxylates from a gold salt.
  • gold oxide or other gold salts could be dissolved in solution with the corresponding carboxylic acid and nitrogen containing groups to create the corresponding amide or polyamide.
  • Au(III) terephthalate was mixed with 1 ,4 - phenylene diamine in alcohol. At 120 °C, the solution was polymerized in less than 5 minutes. At 100 °C, the solution was polymerized in under 10 minutes. Notably, the polymer film is immediately metallized with a gold film on the surface with no byproducts.
  • An alternative gold ink composition is provided, as follows: a gold (III) citraconate salt is synthesized by mixing gold (III) hydroxide with citraconic anhydride (1 : 1.5 to 1 :4) molar ratio as a slurry in methanol. The gold (III) citraconate precipitate is isolated by evaporation of the solvent and washing with methanol. The resulting solid is mixed with a 6: 1 ratio of amylamine to form a translucent solution of gold (III) citraconate. This solution is then deposited on a substrate and heated to 100 °C for 5-10 minutes. At this temperature the solution fully decomposes to metallic gold and forms a continuous, highly conductive film ( ⁇ 0.1 ohms per square (OPS)).
  • OPS ohms per square
  • the numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term "about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the invention may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne une encre à base d'un complexe d'or exempt de particules où un carboxylate d'or est complexé à une amine. Lors du chauffage de la solution, le cation d'or catalyse l'amidation oxydative de l'amine avec le carboxylate pour former un amide à chaîne courte ou polymère tout en réduisant simultanément le cation d'or en or métallique. Ce procédé est extrêmement polyvalent et permet à la fois la préparation de films d'or métallique purs ainsi que des composites d'or polymères ayant des propriétés uniques.
PCT/US2018/045277 2017-08-03 2018-08-03 Compositions d'encres conductrices comprenant de l'or et leurs procédés de préparation Ceased WO2019028436A1 (fr)

Priority Applications (5)

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JP2020505783A JP2020529710A (ja) 2017-08-03 2018-08-03 金を含む導電性インク組成物およびその作製法
US16/636,150 US20200157369A1 (en) 2017-08-03 2018-08-03 Conductive ink compositions comprising gold and methods for making the same
JP2022119494A JP2022136229A (ja) 2017-08-03 2022-07-27 金を含む導電性インク組成物およびその作製法
JP2024075267A JP2024102240A (ja) 2017-08-03 2024-05-07 金を含む導電性インク組成物およびその作製法
US18/806,544 US20250223456A1 (en) 2017-08-03 2024-08-15 Conductive ink compositions comprising gold and methods for making the same

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US62/540,903 2017-08-03

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JP2022136229A (ja) 2022-09-15
US20200157369A1 (en) 2020-05-21
TW201930490A (zh) 2019-08-01

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